US3517042A

US3517042A - Trialkylsilyl (substituted) methyl alkalimetal compounds

Info

Publication number: US3517042A
Application number: US693084A
Authority: US
Inventors: Donald J Peterson
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1967-12-26
Filing date: 1967-12-26
Publication date: 1970-06-23
Anticipated expiration: 1987-06-23

Description

United States Patent O1 zfice Patented June 23, 1970 3,517,042 TRIALKYLSILYL (SUBSTITUTED) METHYL ALKALIMETAL COMPOUNDS Donald J. Peterson, Springfield Township, Hamilton County, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Dec. 26, 1967, Ser. No. 693,084 Int. Cl. C07f 7/02 US. Cl. 260448.2 4 Claims ABSTRACT OF THE DISCLOSURE 1) A process for the conversion of carbonyl compounds -to the corresponding olefins using trialkylsilylorganometallic compounds, and (2) novel trialkylsilylorganometallic compounds prepared for use in the conversion of said carbonyl compounds.

OBJECTS OF THE INVENTION BACKGROUND OF THE INVENTION Several methods are known in the prior art for the conversion of carbonyl compounds to the corresponding methylene derivatives. The most common and most frequently used method for this conversion has the common feature of employing phosphorus-substituted carbanions, the well-known Wittig reagents, which are phosphorus ylids, as the reactive intermediates, see A. W. Johnson, Ylid Chemistry, Academic Press, Inc., New York (1966). The phosphinyl-alkyl metal compounds, L. Horner, H. Holfman, H. G. Wippel, and G. Klahre, Chem. Ber. 92, 2499 (1959), and the phosphonate carbanions, W. S. Wadsworth, Jr., and W. D. Emmons, I. Am. Chem. Soc., 83, 1733 (1961), have also been employed to convert carbonyl compounds to their corresponding olefins. In addition, the alithiophosphonic acid bisamides, E. J. Corey and G. T. Kwiatkowski, J. Am. Chem. Soc., 88, 5652 (1966), and the 0,0'-dialkyl-a-lithiophosphonothio ate esters, E. 1. Corey and G. T. Kwiatkowski, I. Am. Chem. Soc., 88, 5654 (1966), as phosphorus-substituted carbanions also have been used to form olefins from carbonyl compounds. In addition to the or-ganophosphorus compounds, a boron-substituted carbanion, G. Cainelli, G. Dal Bello, G. Zubiani, Tetrahedron Letters, 4315 (1966), a sulfur-substituted carbanion, E. J. Corey and T. Durst, J. Am. Chem. Soc., 88, 5656 (1966), and a silicon-phosphorus-substituted carbanion, H. Gilman and R. A. Tomasi, J. Org. Chem., 27, 3647 (1962), have been used to produce olefins from carbonyl compounds.

Although the course of the reaction and the products obtained will depend on the specific carbanion, hereinbefore described, and carbonyl compound used, the formation of olefins by the use of an heteroatom-substituted carbanion can be summarized as follows using the wellknown Wittig reagents as the carbanion R3'-P-CH2 (!JR2 wherein R and R" are hydrocarbon groups.

SUMMARY OF THE INVENTION v'The present invention relates, primarily to a process consisting of reacting a metalated silane with a carbonyl compound to produce an olefinic compound. The process of the present invention is summarized below as:

wherein R R R R R M and X are as hereinafter defined.

The present invention also relates to novel metalated silanes which can be used in the process of this invention for the preparation of olefinic compounds.

THE SILANES The silanes suitable for the purposes of this invention and which are to be metalated with metalating agents, hereinafter described, are of the general formula wherein R R and R each are saturated alkyl groups having from 1 to about 20 carbon atoms, wherein X is 1) hydrogen, (2) a halogen, such as bromine, chlorine or iodine, or (3) an electron-withdrawing group such as phenyl, methylthio, diphenylphosphino, diphenylthiophosphinyl, and trimethylsilyl groups.

Where X is hydrogen the silane described above is a trialkylmethylsilane;

Where X is a halogen such as chlorine, bromine or iodine, the silane described is a trialkyl(halomethyl) silane, e.g., the trialkyl(chloromethyl)silane, the trialkyl- (bromomethyl)silane, and the trialkyl(iodomethyl)silane; and

Where X is an electron-Withdrawing group selected from the group consisting of phenyl, methylthio, diphenylphosphino, diphenylthiophosphinyl and trimethylsilyl groups, the silane described is a trialkyl(substitutedmethyl)silane, e.g., the trialkyl(phenylmethyl)silane, the trialkyl(methylthiomethyl)silane, the trialkyl(diphenylthiophosphinylmethyl)silane, the trialkyl(dipheny1phosphinomethyDsilane, and the trialkyl(trimethylsilylrnethyl)silane.

Suitable R R and R groups on the trialkylmethylsilanes, the trialkyl(halomethyl)silanes and the trialkyl- (substituted-methyl)silanes and subsequently on the corresponding trialkylsilylmethylmetals, and the trialkylsilyl(substituted)methylmetals prepared upon reaction of the silanes with the appropriate metalating agents, described hereinafter, include straight chain, branched chain and cyclic saturated alkyl groups containing from 1 to about 20 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, Z-methylpropyl, n-pentyl, 2-methylbutyl isopentyl, n-hexyl, Z-methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, n-heptyl, 2,2-dimethylpentyl, n-octyl 2,2-dimethylhexyl, isooctyl, 2-ethylhexyl, n-nonyl, n-decyl, tripropylene, n-undecyl, n-dodecyl, tetrapropylene, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclooctyl, methylcyclohexyl, 2-cyclohexyldodecyl, 12-cyclohexyldodecyl, and dodecylcyclohexyl, said silanes having 40 or less carbon atoms and preferably less than 30 carbon atoms.

For the trialkylmethylsilane the preferred alkyl group is methyl and the preferred trialkylmethylsilane is tetramethylsilane; for the trialkyl(halomethyl)silane the preferred halogen is chlorine, the preferred alkyl group is methyl, and the preferred trialkyl(halomethyl)silane is trimethyl(chloromethyl)silane; and for the trialkyl- (substituted-methyl)silane the preferred alkyl group is methyl, the preferred electron-withdrawing groups are the phenyl and the methylthio groups, and the preferred trialkyl(substituted-methyl)silanes are trimethyl(phenylmethyl)silane and trimethyl(methylthiomethyl)silane.

METALATING AGENTS The metalating agents, hereinafter described, are reacted with the appropriate silanes to prepare the metalated silanes. Since X, as hereinbefore defined, can be a number of diiferent moieties, the preparation of the metalated silanes will depend on the particular silane used as the starting material.

The trialkylmethylsilanes are reacted with a metalating agent selected from the group consisting of an alkylsodium, an alkylpotassium and a complex of an alkyllithium and an alkylenediamine, hereinafter described, to produce the trialkylsilylmethylmetals according to the following:

where M=Na, Li or K; Y==alkyl group. (This method of preparing the trialkylsilylmethylmetals is described in my copending application, Ser. No. 686,291, filed Nov. 28, 1967.

Metalating agents which are useful in metalating the trialkylmethylsilanes are alkylsodiums and alkylpotassiums. The alkylsodiums and alkylpotassiums which are suitable for use in this invention are those wherein the alkyl group is a straight chain or branched chain group containing from 1 to about 20 carbon atoms. The metal atom is preferably attached to a primary carbon atom since the corresponding secondary or tertiary organometallic sodiums and potassiums are difiicult, if not impossible, to prepare.

Suitable alkyl groups for the alkylsodiums and alkylpotassiums are methyl, ethyl, propyl, butyl, 3-methylbutyl, isopropyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, tetrapropylene, 4-propyldecyl, n-hexadecyl, n-dodecyl, and eicosyl.

Alkyllithiums are also suitable metalating agents for use in metalating the trialkylmethylsilanes. The alkyllithiums are preferably selected so that the point of attachment of the lithium is to a primary carbon atom. Alkyllithiums in which the attachment is at a secondary carbon atom can be used, however, they are less effective than those in which the lithium is attached through a primary carbon atom. Alkyllithiums in which the point of attachment is a tertiary carbon atom, e.g., t-butyllithium, are not effective.

Although it is possible to metalate using alkyllithiums alone, the metalation proceeds very slowly. The reactivity of the alkyllithium is increased considerably by complexation with a diamine, hereinafter described, in contrast to the situation with the alkylsodium and alkylpotassium, since their reactivity toward trialkylmethyl silane is not significantly altered by complexation with a diamine. The metalating complex of organolithium compounds and diamines is described by G. G. Eberhardt and W. A. Butte, in J. Org. Chem., 29, 2928 (1964) and A. W. Langer, Jr., in Trans. New York Acad. Sci., Ser. II, 27, 741 (1965).

The diamine compound used in the complexation with the alkyllithium to increase its reactivity is shown as follows:

wherein R R", R and R are saturated straight chain, branched chain or cyclic alkyl groups having from 1 to about 20 carbon atoms. R in the above generic formula is a saturated alkylene straight chain group having from 1 to about 4 carbon atoms with the total carbon atoms in said diamine compound being from about 5 to about 30 carbon atoms. Suitable alkyl groups for R, R, R and R include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, isopentyl, n-hexyl, 2,2-dimethylpentyl, Z-methylpentyl, n-octyl, 2,2-dimethylhexyl, isooctyl, 2-ethylhexyl, n-nonyl, n-decyl, tripropylene, n-undecyl, n-dodecyl, tetrapropylene, n-tridecyl, ethyldodecyl, 2,5,9-trimethyltridecyl, n tetradecyl, n pentadecyl, n hexadecyl, n octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclooctyl, methylcyclohexyl, Z-cyclohexyldodecyl, l2-cyclohexyldodecyl, and 4- dodecylcyclohexyl. The R", R R and R alkyl groups can be the same or different. The preferred R R R and R groups are methyl and ethyl groups.

Suitable R groups include methylene, ethylene, propylene, and butylene groups. The preferred R group is ethylene with methylene and propylene also being preferred. Diamines in which the ring size of the resulting complex with the alkyl-lithium involves 5, 6, or 7 atoms are very effective complexing agents.

Examples of suitable diamine complexing agents include N-methyl,N-ethyl,N'-propyl,N-butylpropylenediamine, N-dodecyl,N,N',N-trimethylmethylenediamine, N-octyl,N,NN'-triethylbutylenediamine, N,N,N',N'-tetraethylpropylenediamine, and N-eicosyl,N,N,N',N,-trimethylethylenediamine.

The preferred diamine complexing agents are N,N,N',N'-tetramethylethylenediamine, N,N,N,N-tetraethylethylenediamine, N,N,N,N'-tetramethylpropylenediamine, and N,N,N',N'-tetraethylpropylenediamine.

The ratio of alkyllithium to the diamine for complexation can be from 1 to 1 to 4 to 1. The preferred ratio is The trialkyl(halomethyl)silanes are reacted with a metalating agent which is an alkali metal or an alkaline earth metal such as lithium, sodium, potassium or magnesium to produce the trialkylsilylmethylmetals according to the following:

where X=Cl, Br or I; M:Li, Na, K or Mg; M'=Li, Na, K or MgX. (This method of preparing the trialkylsilylmethylmetals where M is Mg is described in J. R. Gould, L. H. Sommer and F. C. Whitmore, J. Am. Chem. Soc., 70, 2874 (1948)).

The metalating agents which can be used to react with the trialkyl(halomethyl)silanes to form the trialkylsilylmethylmetals are metallic sodium, metallic potassium, metallic lithium and metallic magnesium. The preferred metalating agent for the trialkyl(halomethyl)silanes is magnesium metal.

The trialkyl(substituted-methyl)silanes are reacted with a metalating agent which is an alkylor aryl-sodium, an alkylor aryl-potassium, and an alkylor aryl-lithium, or

a complex of an alkyllithium and an alkylenediamine, hereinbefore described, to produce the trialkylsilyl(substituted) -methylmetals according to the following:

where X is an electron-with-drawing group hereinbefore described; M=Na, K or Li; Y=an alkyl group or aryl group. [Where X, R R and R are phenyl, this method of preparation is described in H. Gilman and H. Hartzfeld, J. Am. Chem. Soc., 73, 587 8 (1951).]

Suitable metalating agents for reaction with the trialkyl- (substituted-methyl)silanes to form the trialkylsilyl(substituted)-methylmetals are alkylor arylsodiums, potassiums or lithiums, wherein the alkyl or aryl group contains from 1 to about 20 carbon atoms, and the complexes of the alkyllithiums and the diamines hereinbefore described. Because of the fact that in the trialkyl(substituted-methyl) silane an electron-withdrawing group is present, a greater variety of alkylor arylsodiums, potassiums, and lithiums are reactive towards these silanes. The preference for attachment for the alkali metal to the primary carbon atom is not as great as in the situation hereinbefore described with the trialkylmethylsilane.

Suitable alkyllithiums, alkylsodiums, and alkylpotassiums for use as the metalating agent are those wherein the alkyl groups are straight chain, branched chain and cyclic containing from 1 to about 20 carbon atoms, e.g., methyl, ethyl, propyl, n-butyl, 3-methylbutyl, isopropyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, tetrapropylene, 4-propylundecyl, n-hexadecyl, n-dodecyl, eicosyl, cyclohexyl, cyclopentyl, and methylcyclohexyl.

Suitable aryl groups for use in the arylsodiums, potassiums and lithiums are the following: phenyl, biphenyl and naphthyl groups and the substituted aryl groups such as tolyl, xylyl, and decylphenyl. Aralkyl or alkaryl groups such as phenyldecyl, butylphenyl, and 4,4-diphenylbutyl are also suitable.

The preferred metalating agents for the trialkyl(substituted-rnethyl)silanes are n-butyllithium and the complexes of the alkyllithiums with the diamines hereinbefore described as preferred for metalating the trialkylmethyl silanes.

'Ihe metalating agents are normally sold commercially with an excess of a liquid saturated hydrocarbon such as pentane, hexane, octane, cyclohexane, isooctane, nonane, or decane. However, any saturated hydrcarbon having from 5 to 16 carbon atoms and being either straight chain, branched chain or cyclic can be used. The concentration of the metalating agent is usually about 1.5 molar and can range from 1 molar to 3 molar concentration. In addition to the saturated hydrocarbon solvents, ether solvents such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane can also be used in the metalating step. The preferred solvent is hexane because the boiling point is optimum and thus it is easily removed by distillation without any adverse effects on the metalated silane. Other preferred solvents are pentane and heptane. Tetrahydrofuran is also preferred.

The metalation reaction must take place in an inert atmosphere, e.g., nitrogen, argon, or helium since the organometallic compounds are highly reactive and 'will be decomposed if exposed to a reactive atmosphere, such as air or moisture. The preferred inert atmosphere is argon.

The temperature of the reaction can be any temperature at which the reaction mixture is liquid, i.e., above about -60 C. The temperature is usually less than about 100 C. since organometallic compounds tend to decompose above this temperature. The preferred temperature is about 20 C. (room temperature).

A stoichiometric amount or an excess of the silane in relation to the metalating agent is preferably employed to prevent excess metalating agent from interferring with the subsequent reaction with carbonyl compounds. If excess metalating agent is present it is readily reacted with and competes in subsequent reactions with the carbonyl compounds. The silane can even be used as the reaction medium in ratios as high as 4:1 with respect to the metalating agent.

Where X, in the trialkyl(substituted-methyl)silanes, is the diphenylthiophosphinyl group, the diphenylphosphino group, the trimethylsilyl group or the methylthio group, and these silanes are metalated to form the lithium, sodium or potassium organometallics, the resulting compounds are new classes of compounds. These new classes of compounds are specifically the trialkylsilyl- (diphenylthiophosphinyl)methylmetals, the trialkylsilyl- (trimethylsilyl)methylmetals, the trialkylsilyl(diphenylphosphino)methylmetals and the trialkylsilyl(methylthio)methylmetals. All of these compounds are useful to produce known substituted olefins. For example: where trialkylsilyl(diphenylphosphino)methylmetal is reacted with benzaldehyde, B styryldiphenylphosphine, (C H PCH=CHC H a known compound [see D. Gloyna and H. G. Henning, Angew. Chem. Internat. Edit, 5, 847 (1966)] is obtained; where trialkylsilyl- (methylthio)methylmetal is reacted with benzaldehyde, CH SCH CHC H 8-styryl methyl sulfide, a known compound [see M. C. Caserio, R. E. Pratt and R. J. Holland, 1. Am. Chem. Soc., 88, 5747 (1966)] is obtained; where trialkylsilyl(trimethylsilyl)methylmetal is reacted with benzaldehyde, (CH SiCH=CHC H 18- styryltrimethylsilane, a known compound [see L. H. Sommer et al., J. Am. Chem. Soc., 76, 1613 (1954)] is obtained. [(R -R R )SiCH=CHC H is also formed] CARBONYL COMPOUNDS The carbonyl compounds which are useful and can be advantageously employed in this invention are of the following general formula:

wherein each R and R is selected from the group consisting of hydrogen and alkyl, aryl, alkaryl, aralkyl, cycloalkyl and, where R is taken together with R bivalent alkylene groups, said groups having from 1 to about 30 carbon atoms, said carbonyl compound containing 40 or less carbon atoms and preferably less than 30 carbon atoms. Upon reaction with the carbonyl compound the metalated silanes yield olefins of the following general wherein R R and X (except not a halogen atom) are as hereinbefore described.

Where R and R are alkyl groups suitable groups are as follows: methyl, ethyl, n-propyl, isopropyl, n-pentyl, isopentyl, n-hexyl, 2,2-dimethylpentyl, n-heptyl, n-octyl, 2,2-dimethylhexyl, isooctyl, 2-ethylhexyl, n-nonyl, n-decyl, tripropylene, n-undecyl, n-dodecyl, tetrapropylene, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, methylcyclohexyl, 2-cyclohexyldodecyl, l2-cyclohexyldo'decyl, 4-dodecyclohexyl, and cyclooctyl groups.

Other suitable R and R groups include aryl groups such as phenyl, biphenyl, and naphthyl groups and substituted aryl groups such as tolyl, dodecylphenyl, 2-methyl-4- biphenyl, 4-methyl-1-naphthyl, 4-octyl-2-naphthyl, and 2, 4 dimethylphenyl groups. Still other examples of suitable groups for R and R include aralkyl groups such as 3- phenyldodecyl, 4-phenyloctyl, 4-phenyldecyl, 4-phenylbutyl, 4-tolylmethyl, 3-(2-naphthyl)propyl, 4-(l-naphthyl) butyl, 3-biphenylpentyl, and 3-biphenylpropyl groups.

Other substituted R and R groups which are suitable include 3-(p-tolyl)propyl, 4-phenylbutyl, 4-(1-naphthyl) hexyl, 3-(ethylnaphthyl)propyl, 3-(4-biphenyl)propyl, 3- (dimethyl)propyl, and 3,3-diethylhexyl. Where R and R are taken together, as a bivalent alkylene group, suitable bivalent alkylene groups are ethylene, propylene, butylene, pentalene, octalene, decalene, hexadecalene and eicosalene.

Phenyl and methyl are preferred as the R and R groups. Also preferred are alkyl groups having from 1 to 8 carbon atoms in each R and R group.

The reaction of the rnetalated silane with the carbonyl compound is carried out in an inert atmosphere such as argon, although nitrogen and helium are also suitable and preferred. The reaction is normally conducted in a solvent medium and at a temperature of from about 60 C. to about 100 C. The preferred temperature is about 20 C. (room temperature). Suitable solvent mediums are saturated hydrocarbons having from about 5 to 16 carbon atoms such as pentane, hexane, heptane, octane, isooctane, cyclopentane, cyclohexane, and cycloheptane and aromatic hydrocarbons such as benzene, toluene, and xylene. Ether solvents such as tetrahydrofuran, dioxane, 1,2- dimethoxyethane, dibutyl ether and diethyl ether are also suitable for the purpose of this invention as solvents. Ether solvents such as tetrahydrofuran are preferred.

In some cases on reaction of the carbonyl compound with the rnetalated silane a relatively stable metal alkoxide is formed. For example, the magnesium (Grignard) entity, (R R R )SiCH MgX, forms a magnesium alkoxide, which on acidification with dilute ammonium chloride yields the (,B-hydroxyalkyl)trialkylsilane. The (fl-hydroxyalkyl)trialkylsilane is converted to the corresponding olefin by reaction with sodium or potassium hydride or potassium-t-butoxide. The conversion of the (p-hydroxyalkyD- trialkylsilane to the sodium, potassium, or butoxide intermediate to form the olefin is preferred in some cases because of kinetic considerations, i.e., where the decomposition of the alkoxide into the olefin is slow.

In the reaction of the trialkylsilyl organometallic with a carbonyl compound, the following well-known compounds are produced:

(a) Where benzophenone is reacted with a trialkylsilylmemthylmetal styrene is produced, which is a wellknown monomer useful in the manufacture of plastics, synthetic rubbers and resins;

(b) Where octanal is reacted With a trialkylsilylmethylmetal l-nonene is produced, which is useful in organic synthesis, as a wetting agent and as a lubricating oil additive, see Elizabeth and Arthur Rose, Condensed Chemical Dictionary, 7th Ed., p. 677, Reinhold, New York, 1966;

(c) Where acetone is reacted with a trialkylsilylmethylmetal, isobutylene is produced and the isobutylene is useful in the production of isooctane, butyl rubber, polyisobutene resins and copolymer resins with butadiene and acrylonitrile, see Condensed Chemical Dictionary, op. cit. supra, p. 518.

Other compounds produced by utilizing this invention are known compounds as shown by the cited references, e.g.:

(a) The reaction of benzophenone with a trialkylsilyl- (pheuyl)methylmetal produces triphenylethylene, see Heilbron, Dictionary of Organic Compounds, vol. 5, p. 3199, Oxford University Press, 1965;

(b) The reaction of acetone with a trialkylsilyl- (phenyl)methylmetal produces 8,13-dimethylstyrene, see Heilbron, vol. 4, p. 2300, op.cit. supra;

(c) The reaction of benzophenone with a trialkylsilylmethylmetal produces 1,1-diphenylethylene, see The Merck Index of Chemicals and Drugs, 7th Ed., p. 381, Merck & Co., Rahway, N.J., 1960;

(d) The reaction of a trialkylsilyl(trimethylsilyl)- methylmetal with benzaldehyde produces fl-styryltrimethylsilane, see E. A. Chemphev and N. G. Tolstikova, Isv. Akad. Nauk SSSR, Otd. Khim. Nauk, pp. 1223 8, (1962) [C.A., 58, 5712h (1963)];

(e) The reaction of a trialkylsilyl(diphenylphosphino)- 8 methylmetal with benzaldehyde produces B-styryldiphenylphosphine, see H. Holfmann and H. J. Diehr, Chem. Ber., 98, 363-8 (1965);

(f) The reaction of a trialkylsilyl(methylthio)methylmetal with benzaldehyde produces fl-styryl methyl sulfide, see G. Wittig and M. Schlosser, Chem. Ber., 94, 1373-83, (1961);

(g) The reaction of a trialkylsilyl(phenyl)methylmetal with cyclohexanone produces cyclohexylidenephenylmethane, see S. Trippett and D. M. Walker, J. Chem. Soc., 1266, (1961).

As can be seen by the above, compounds produced by the process of this invention are useful in many waysparticularly in the synthesis of polymeric materials useful as plastics, resins and synthetic rubbers.

All parts, percentages and ratios herein are by weight unless otherwise specified. The following examples are illustrative of the invention and should not be taken as limiting the scope of the claims.

EXAMPLES General All reactions and procedures hereinafter described were performed in an atmosphere of oxygen-frfee argon. The nmr spectra were obtained on Varian Associates HR-60 (phosphorus) and HA-IOO (proton) spectrometers. The infrared spectra were obtained on a Parkin-Elmer Infracord spectrometer. The gas-liquid phase chromatography was done on an Aerograph instrument using a SE-30 column on Chromosorb W. The mass spectrographic analyses were obtained on an Atlas CH-4 mass spectrometer.

The following example, given generically, sets forth the procedure followed in the examples referred to in the tables which are to follow hereafter. The tables which follow each step refer to the step of the procedure which precedes it, e.g., the rnetalated silanes prepared in step (a) are summarized in Table I immediately following step (a) and the olefins prepared in step (b), by reaction of the rnetalated silanes with the carbonyl compounds, are summaribed in the Table II immediately follownig step (b). The two tables are co-ordinated through the corre Spondence of the example numbers, e.g., Example 1 in Table I, step (a) continues as Example I in Table II, step (b).

(A) PREPARATION OF METALATED iSILANES (1) Halomethylsilanes.0.05 mole of the trialkyl (halomethyl)silane in 50 ml. of hexane was added dropwise to 0.1 g. at. wt. of an alkali metal (e.g., sodium, lithium, or potassium) dispersed in 50 ml. of hexane or of magnesium ribbon suspended in 50 ml. of tetrahydrofuran under a blanket of argon. The unreacted metal was filtered off subsequently.

(2) Methylsilanes.0.05 mole of the trialkylmethylsilane in 50 ml. of hexane was added to 0.05 mole of (1) an alkylsodium, (2) an alkylpotassium, or (3) a complex of an alkyllithium and an N,N,N',N'-tetraalkylalkylenediamine, prepared by mixing equal molar amounts (0.05 mole) of the alkyllithium and the diamine. The reaction was stirred for three days at room temperature.

(3) (substituted-methyl)silanes.0.05 mole of trialkyl (substituted-methyl) silane in 50 ml. of hexane was added dropwise to 0.05 mole of 1) an alkylor arylsodium, (2) an alkylor aryl-potassium, (3) an alkylor aryl-lithium, or (4) a complex of an alkyl-lithium and an N,N,N',N'-tetraalkylalkylenediamine prepared as in sub-step (2) of step (a) above and subsequently stirred for 1 to 4 hours.

The trialkylsilylmethylmetals, as prepared in sub-steps (l) or (2) above of step (a) above, the trialkylsilyl(substituted)methylmetals, as prepared in sub-step 3) of step (a) above, or the trialkylsilylmethylmagnesium halide (Grignard), as prepared in sub-step (l) of step (a) above, were analyzed either using H NMR spectroscopy,

P spectroscopy or IR spectroscopy or, in some cases they were deuterated and then analyzed using a mass spectrograph, to confirm the presence of the metalated 1 tributylsilyl (diphenylphosphino)methylsodium, cyclohexylidimethylsilyl(diphenylthiophosphinyl)- methylpotassium,

silane. dodecyldlmethylsilyl(trimethylsilyl)methyllithium,

TABLE I Step (a)-Preparation of the metalated silane Metalated silane preparation Example Silane Metalating agent method Metalated silane formed 1 (CH3)3SlCH2Cl Mg Sub-step (1) (cHmsiCHzMgCl H3)3SlCHzC1 Mg ..-..(10 (CH3)3SiCHzMgCl (OH SiCH2C1 Mg (CHs)aSiOH2MgOl (CH3 3SiCHzCl Mg (GH SiCH MgCl (CH SiCHzCl Mg (CHahSiCH MgCl (CH3)3SiCH2CeH5 I1-C4HgLl-TMEDA (C 3)3siCH(CH5)(Li) (CH3)3S1CH2C5H5 ll-C4HgLl-TMEDA. (CH SiCH(G H )(Li) (0113):;8101120 11 n-CsEhLi-TMEDA (CH3)aSiOH(CsH )(Li) 0H3)3SiGHgC5H5 11-0 H Li-TMEDA (CHa)3SiCH(CsH )(Li) a)a i 2P(CaHt)z n-C4 o i sh iCHlH s mKLi) 11.- (CH )3S1CH P(C0H5 2 11-C4H9L1 (C 3)3SlCH[P(CaH5)z](Li) 12.- (CH3)3S1GH2P(S)(C5H5)2 n-CiH Li (CH3)5S1CH[P(S)(C H5)fl](Li) 13 (CH3) S1CH2SCH3 n-C4HnLi (CH3)sSiCH(SCH )(Li) 14 (CH S1CH2SCH3 1'1-C4H9Li do (CH3)aSiCH(SCH )(Li) 15 (CH3)3SiCH3 n-OrHoLi-TMEDA Sub-step (2) (CHshSlCH Li 1 N,N,N,N-tetramethylethyleuediamine When in step (a) of Examples 1-5 above other trialkyl(halomethyl)silanes are substituted on a molar basis for the trimethyl(chloromethyl)silane or when sodium, potassium, or lithium is substituted on an equivalent basis for the magnesium as the metalating agent, substantially equivalent results are obtained in that the corresponding trialkylsilylmethylmetals are obtained, e.g.,

trimethylsilylmethyllithium, triethylsilylmethylpotassium, ethyldimethylsilylmethylsodium,

2,2-dimethyl hexyldimethylsilylmethyllithium, tributylsilylmethylpotassium, cyclohexyldimethylsilylmethylpotassium, and dodecyldimethylsilylmethylsodium.

When in step (a) other trialkyl(substituted-methyl)- silanes are substituted on a molar basis for the trimethyl- (phenylmethyl)-silane of Examples 6-9, for the trimethyl (diphenylphosphinomethyl)silane of Examples 10-11, for the trimethyl (diphenylthiophosphinylmethyl) silane of Example 12, or for the trimethyl(methylthiomethyl)- silane of Examples 13 and 14; or when other metalating agents such as alkylor aryl, sodiums, potassiums, or lithiums are substituted on a molarjbasis for the metalating agents used, i.e., for the n-C H Ii-TMEDA complex in Examples 6-9 or for the n-C H Li in Examples 1014, e.g., methyl, ethyl, propyl, n-butyl, n-pentyl, n-decyl, n-dodecyl, eicosyl, phenyl, tolyl and naphthyl sodiums, potassiums and lithiums, or when other complexes of alkyllithiums with N,N,N',N'-tetraalkylalkylenediamines are substituted on a molar basis for the n-butyllithium-TMEDA complex, e.g., the complexes of methyl, ethyl, propyl,

n-pentyl, n-octyl, n-decyl, n-hexadecyl and eicosyl lithiums with N-methyl,N-ethyl,N'-propyl,N'-butylpropylenediamine, N-dodecyl,N,N',N-trimethylmethylenediamine, N-0ctyl,N,N,N-triethylbutylenediamine, N,N,N,N'-tetraethylpropylenediamine, or N-eicosyl,N,N,N-trimethylethylenediamine,

substantially equivalent results are obtained in that the corresponding trialkylsilyl(substituted)methylmetals are obtained,

trimethylsilyl (phenyl)methylpotassium,

trimethylsilyl(phenyl)methylsodium,

trie'thylsilyl(phenyl)methyllithium,

triethylsilyl (methylthio) -methylpotassium,

ethyldimethylsilyl(methylthio)methylsodium,

(2,2-dimethylhexyl)dimethylsilyl(trimethylsilyl) methyllithium,

de cylidimethyl trimethylsilyl) methyllithium,

cyclopentylhexadecylmethylsilyl(diphenylphosphino)- methylpotassium, and

propyl (Z-methylbutyl)methylsilyl(methylthio)- methylsodium When in step (a) above, other trialkylmethylsilanes are substituted for the tetramethylsilane of Example 15, e.g., triethylmethylsilane, ethylbutyldimethylsilane, dodecyltrimethylsilane, eicosyldipropylmethylsilane, cyclohexyldodecyldimethylsilane, (2,2-dimethylbutyl)trimethylsilane, (cyclohexyl)decylidbutylmethylsilane; or other metalating agents such as alkylsodiums or potassiums are substituted on an equivalent basis for the complex, e.g., methyl, ethyl, propyl, n-butyl, n-pentyl, n-decyl, n-dodecyl, eicosyl, phenyl, tolyl and naphthyl sodiums, potassiums and lithiums, or other complexes of alkyllithiu-ms with N,N,N',N-tetraalkylalkylenediamines substituted on a molar basis for the n-C H Ii-TMEDA complex, e.g., the complexes of methyl, ethyl, propyl, n-pentyl, n-octyl, n-decyl, n-hexadecyl and eicosyl lithiums with N-methyl,-N-ethyl,N'-propyl,N-butylpropylenediamine, N-dodecyl,N,N',N'-trimethylmethylenediamine, N-octyl,N,N,N'-triethylbutylenediamine, N,N,N,N-tetraethylpropylenediamine, and N-eicosyl,N,N,N'-trimethylethylenediamine,

(B) REACTION OF THE MFIIALATED :SILANE WITH THE CARBONYL COMPOUND The following generic procedure was used in step (b) summarized in Table II hereinafter. The reaction mixture containing the metalated silane (refer to Table I, Ex-

amples 1-15 for more specificity) as prepared in step (a) above, was added dropwise and with stirring to an equivalent amount (0.05 mole) of the carbonyl compound,

12 was formed. This was converted to an unstable intermediate, the alkali metal alkoxide, by reaction of the indicated alcohols with an equal molar amount (0.05) of sodium or potassium hydride or potassium-t-butoxide, as indicated, which upon elimination formed the specified see Table II hereinafter, dissolved in 50 ml. of tetrahydro- 5 corresponding olefins [(R) (R )C=CHX]. Conversion furan. The mixture was stirred for 30 minutes to 24 to the alkali metal alkoxide in some cases (Example 15) hours. The temperature was maintained below the reflux other than when the Grignard reagent was used was retemperature by means of a water bath. On a workup, quired. This was accomplished as described in step (c) the olefin formed [(R (R )C CHX], wherein R R above.

TABLE II Step (b)-Reactin of the Metalated Silane with the carbonyl compound Step (I) Carbonyl Yield, Method of analysis Ex. compound Intermediate isolated Base used Olefin isolated Percent (see key below) it 1 0 11200611 (CH3)3SiCH2 (0H)( 6 5)2 KH (CaH5)2C=CH2 86 (I). {3),(4).

H 2 0511500511 (CHa)aSlCH C(OH)(CaHs)z NaH (OBH5)ZC=CH2 G7 1).(.'n,(4).

ll 3 C5I-I5GH (CHmSiCHzCKH) (OH) (C0115) KH Polystyrene 2 91 (3), (4).

if 4 nC1H15CH (CHmSiCHzCU-I)(0H)( 1--C1 KH Il-C7H15CH=CH2 70 (1),(3),(4).

1i 5 CH CCH; (CH SiOH C(OH)(CHa): tC H OK (CH C=CH (3)+conversi0n to dibl'omido. ii 6 C H GCQH None None (CsH5)2C=CH(C6H5) 77 (1).(3).(4).

ii 7 ofimon --d0 .d0 (CuH5)OH=CI-I(CoI-I5) 72 (3).).

i1 8 CHaCCHa d0 d0 (CaHs) CH=C(CHa)z (1),(3),(4).'

9 cC H C=O do .d0 CC5H10C=CH(C,H5) 5 (1),(3).

I? 10 C H CH ...do do [(C0H5)2 ]C =C (Co 5) 5d ),(2),(3),(4)-

H 11 coHscce s -----d0 "do [(CaH5)2P]CH=C(CeH5)z (1), (2), (3),

ll 12 C5H5GC6H5 ..-do ..d0 (Ce 5)z (S)C =C(Cs 5)z 8 (1),(2),( ,(4), C, 79.4; H, 5.5

II 13 CaH OH d0 .410 (CHaSCH=CHCsHs)z 64 (1 ,(a 4

ii 14 CoHsCCeHs do do CHaSCH=C(CaHs)z 56 (1),(3),(4),O,79 8,

II 15 OH COH (CH SiCHzC(0H)(CHa)z KH (CH3)zC=OHz 25 (1).

1 Where stereoisomerism is possible, 1 :1 ratios of cis to trans obtained.

(l) H NMR, (2) P NMR. ('3) IR. (4) gepc.

and X are as hereinbefore described except that X is not a halogen atom], was analyzed and its structure confirmed using either H NMR, P NMR, IR spectroscopy or gas-liquid phase chromatography.

(C) CONVERSION OF THE MAGNESIUM ALKOXIDE TO THE OLEFIN Where the metalated silane was the magnesium (Grignard) reagent, (Examples 1-5) prepared as in substep (1) of step (a) above, and was subsequently reacted with a carbonyl compound,

as specified in Table II, and hydrolyzed with dilute aqueous ammonium chloride, the indicated (2-hydroxyalkyl)trialky1silane or (2-hydroxyaralkyl)trialkylsilane 2 Polymerized on Workup.

13 What is claimed is: 1. Trialkylsilyl(substituted)methylmetal having the formula compounds wherein R R R each are saturated alkyl groups containing from 1 to 20 carbon atoms, wherein X is selected from the group consisting of methylthio, diphenylthiophosphinyl, diphenylphosphino, and trimethylsilyl groups, wherein said compounds contain 40 or less carbon atoms, and wherein M is selected from the group consisting of Li, Na, and K.

2. The compounds of claim 1 wherein R R and R each are alkyl groups containing from 1 to about 12 carbon atoms.

14 3. The compounds of claim 1 wherein R R and R are methyl. h

4. The compounds of claim 1 wherein M is lithium.

References Cited UNITED STATES PATENTS 3,293,275 12/ 1966 Pratt 260448.2 3,293,275 12/1960 Pratt 260448.2 3,426,021 2/ 1969 Seyferth 260448.2

TOBIAS E. LEVOW, Primary Examiner W. F. W. BELLAMY, Assistant Examiner "H050 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 517,042 Dated June 23, 197 0 Inventor(s) Donald J Peterson g 1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

" should be --R '-EH '1 i column 2 lines 3-7, "R F -CH Column 4, line 43, "Neicosyl,N,N,N',N',trimethylethylene() diamine" should be Neicosyl,N,N',N'-trimethylethylenediamine--.

Column 8, line 25, "frfee" should be -free--.

Column 8, line 28, "Parkin-Elme-" should be Perkin-Elmer.

Column 8, line 42, "summaribed" should be -summarized.

Column 8, line 42 "follownig" should be -following Column 9, line 48 "n-C H Ii TMEDA" should be -nC H Li TMEDA- Column 10, line 2 "cyclohexylidimethylsilyl (diphenylthio phosphinyl)methylpotassium" should be -cyclohexyldimethyl() silyl(diphenylthiophosphinyl)methylpotassium-.

Column 10, line 35, "(cyclohexyl)decylidbutylmethylsilane" should be -(cyclohexyl)decyldibutylmethylsilane.

Column 10, line 45, "nC H Ii 'IMEDA" should be --nC H Li TMEDA-- Column 11 Table II Example 1, Q should be c H c H c O H UZC H 3 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 517 ,042 Dated June 23 1970 Donald J. Peterson Page 2 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Inventor(s) Column ll Table II Example 9 "cC H C CH (C ,H should be -c C H C CH(C H Column ll, Table II, Example 13, (CH SCH CHC H should be -CH SCH CHC H Column 11, Table II, line 59, "gepc" should be glpc.

Gill AM QEMH" unv 24m (SEAL Meat:

MH- Flewher, Jr. mm H: I Q Offieer commissioner of Patanta